Production of amide acid sulphates from nitriles



.'acid mono-hydrate. droxy group is substituted in this to give TE-S HALF B. TRUSLEE, OF PITTSBURGH, PENNSYLVANIA, ASSIGNOR TO THE ROESSLER d6 HASSLACHER CHEMICAL COMPANY, OF NEW YORK, N. Y1, A CORPORATION. 011' NE YORK.

rnopucrron or AMIDE ACID suLrrmrEs FROM mrrarnns.

No Drawing.

To all whom it may concern-.-

Be it known that I, RALEB. TRUsLnR, a citizen of the United States, and resident of 1321 Tennessee Ave, Dormont, Pittsburgh, in the county of Allegheny and State of Pennsylvania, have invented certain new and useful Improvements in the Production of Amide Acid Sulphates from Nitriles, of which the following is a specification.

It has long been known that nitriles can be hydrolyzed by alkalis or acids, producing more or less quantitatively (1) in the first. case, an alkali salt of an acid corresponding to the nitrile with the liberation of ammonia, and .(2) in the second case, an acid corresponding to the nitrile, together with an ammonium salt.

l[ have made adeparture from these methods of hydrolysis of nitriles and have discovered a means for partially hydrolyzing nitriles by sulphuric acid monohydrate whereby the IllllI'llB'lS converted into an amide acid sulphate.

l have found that there are several classes of nitriles of the formula R-CN some members of which decompose when treated with sulphuric acid monohydrate, or partially decompose before hydrolysis is complete.

Some of these nitriles are Well knowncompounds, such as the sugar cyanohydrins, while others are little known, such as the nitriles formed by' condensing ethylidene aniline with HCN. The individual nitriles which cannot be treated by this method are so varied that they cannot be placed under any one heading.

A straight chain aliphatic nitrile of the formula vis easily and'nearly quantitatively converted into'the amide acid sulphate by sulphuric If, however, one hya hydroxy nitrile as Y H n n the compound still can be hydrolyzed in the same manner with but little decomposition,

Application filed July 22, 1925. Serial No. 453%.

to give a hydroxy amide acid sulphate. However, if two-or more adjacent hydroxyls occur as,

with sulphuric acid monohydrate. For example,

if have therefore chosen to designate R in my general formula lit-(3N as standing for hydrogen or for any, monovalent aliphatic,

cyclic or aromatic group or derivative there- 'of indllferent to the action of sulphuric acid monohydrate. In this way I limit the applicat1on to those nitriles wherein the group R is so little attacked by sulphuric acid monohydrate as not to seriously interfere withthe yields of the amide acid sulphates and l designate this limitation in the .claims by the phrase indifferent to the action of sulphuric acid monohydrate.

By reacting a nitrile limited as above and represented by the formula Rj-CN with su phuric acid monohydr'ate, a reaction product comprising an amide acid sulphate is obtained to which the formula may be assigned. Sulphuric acid monohydrate is defined here as the acid whose composition is represented by thev formula mso n o. a

I' have discovered also, that a considerable saving in the time required for the conver- 'sion-of a nitrile into an amide acid sulphate isefi'ected by the addition of a small amount liquid ma be added to and mixed with re actants w ich consist of a nitrile and sulphuric acid monohydrate, with or without a halide of the type AX just defined, for the purpose of obtaining the'amide and sul phate in a divided state.

For the purpose of illustrating my discoveries Igive the following examples 2-- Ewample [.-One.mol of hydrogen cyanide, weighing 27 grams and 1 mol of sulphuric acid monohydrate weighingaipproximately 116.1 grams to which the ormula H SO .H O has been assigned, are both cooled to prevent loss of the hydrogen cyanide by volatilization and too rapid reaction when thetwo components are mixed. The two reactants are then mixed by adding one to the other with stirring and preferably with cooling. The mixture which is liquid and completely miscible and homogeneousis.

allowed to react while it is kept cool.- The temperature may vary throu h a wide range, but temperatures from 0 to 10 'C. are suitable. After an indefinite time, some times extending to 7 days, crystals begin to form in-the liquid which has in the meantime become more viscous, and finally the entire mixture'becomesa solid, white, crystalline mass.

The conversion of. hydrogen cyanide to formamide acid sulphate may be illustrated by the equation:

Analysis of the crystalline compound has shown it to be composed of the-following elements in the percentages given, subject Furthermore, it has been found that both' form'amide and sulphuric acid may be separated from-the compound by known chemi'; cal means. I

Ewample H.One-mol of hydro cyanide weighing 27 am and 1 mo of sulphuric acid mono drate weighin 116.1

grams are cooled an -mixedand to t e mixture is added one-tenth to two-tenths ofqa gram of ammonium chloride." The reaction mixture is permitted to react in the cold. After an indefinite period of standing varying from a few hours, to approximately 24 hours, the liquid reactants are converted into crystalline formamide acid sulphate. I do not wish to limit myself to the weights of catalyst here given, nor to the period of. time allotted for the reaction, for it is understood that the period for reaction is shorter when more of the catalyst is used, and in comparison, is longer if the reaction is conducted at lower temperatures.

Example I H .One mol of hydrogen cyanide weighing 27 grams and 1 mol of sulphuric acid monohydrate weighing 116.1

grams are cooled and mixed and to this mixture are added two-tenths of a,gram of sodium chloride and an arbitrary amount of carbon tetrachloride, in this case 200 cc. The mixture is stirred during the period of reaction. The crystals of formamide acid p cyanohydrin (lactonit-rile or alpha-hydroxy.

propionic nitrile) weighing 71.06 grams and 1 mol of sulphuric acid monohydrate weighinghabout 116.1 grams are cooled and mixed. A omogeneous solution results. To this a catalyst consisting of 0.2 gram of sodium fluoride may be added. The liquid is then graduall warmed so that in the course of about 8 ours a temperature of 70 C. has been reached.

By this time the liquid has become more viscous and of syrupy consistency, and no lhonge'r is composed essentially of acetalde- LY hydroxy propionic nitrile) and sulphuric acid.monohydrate, but is mainly composed of lactamide acid sulphate.

The nature of the reaction which takes place "between acetaldehyde cyanohydrin and sul huric acid monohydrate may be represente by the equation:

just descri d is allowed to stand for a long period of time, crystallization will occur,

whereby there will beobtained a white,

which is here defined as lactamide acid sul hate. a

he reaction productconsisting of lactamide acid sulphate maybe separated by known chemical means into a sulphate and. lactamide.

I do not wish to restrict the use of my process to the limits of temperature and time heregiven, for I have found that the conversion of the nitrile takes place at temperatures below 0 C. and above 70 C. and that the time required for the reaction vae cyanohydrin (lactonitrile or alpha homogeneous solution results.

sulphuric acid monohydrate.

ries with changes of both temperature and catalyst.

Ewample V.One mol of benzo nitrile weighing about 103.08 ams and one mol (of sulfiphuric acid mono ydrate are preferably rst cooled, and then mixed until a Two-tenths of a gram of aniline hydrochloride are then stirred in as a catalyst. The reaction mixture is then gradually heated to about C. during about two hours, and thence to about 7 0 or Ch during about another hour. By this treatment, the liquid benzonitrile is converted into a solid compound which has been found to consist essentially of benzamide acid sulphate, which is here represented by the formula where qS represents the phenyl group, as deby standard chemical texts. The course of the'reaction is illustrated From the benzamide acid sulphate, benzamide may be obtained. For example?- Pulverized benzamide acid sulphate is stirred into ammoniacal alcohol. The sulphuric acid constituent of benzamide acid sulphate is neutralized by the ammonia and remains as an insoluble precipitate while benzamide is taken into solution in the alcohol. By evaporating the alcohol, benzamide is recovered.

Claims:

1. The addition product of a nitrile and 2. A stable compound comprising an amide acid sulphate of the general formula a-c-nmnisoi in which R represents an organic radical indifferent to the action of sulphuric acid monohydrate.

3. Formamide acid sulphate represented, by the formula 4. The. rocess of partiall hydrolyzin a nitrile 0% the general for i nula RCN wherein R represents an organic radical diiferent to the action of sulphuric acid monohydrate, by treatment with sulphuric acid monohydra-te.

5. A process consisting in partially hydrolyzing a nitrile of the generalformu a R-ON, wherein R represents an organic hydrate by sulphuric acid monohydrate in the presence of a salt of a halogen .acid.

7. A process consisting in partially hydrolyzing a nitrile of the general formula R-CN, wherein R represents an organic radical indifl'erent to the action of sulphuric acid monohydrate, by sulphuric acid monohydrate in the presence of a salt of a haloliquid. I

8. A process consisting in, partially bydrolyzing a nitrile of the general .formula R-GN, wherein R radical indifferent to the action of sulphuric acid monohydrate, by sulphuric acid monohydrate in the presence of a salt of a halogen acid and while suspended in carbon tetrachloride.

9. A process consisting in partially hydrolyzing a nitrile of the general formula RON, wherein R represents an or anic radical indifferent to the action of sulp uric acid monohydrate, by sulphuric acid monohydrate in the presence of sodium chloride.

10. A process consisting in partially h drolyzing a nitrile of the general formu a R-CN wherein R represents an or anic' radical indifferent to the action of sulp uric acid monohydrate by sulphuric acid monohydrate in the presence of sodium chloride and while suspended in carbon tetrachloride.

11. A process consisting in partially hygen acid and while suspended in an inert represents an' organic drolyzing HGN by sulphuric acidmonohydrate.

12. A process consisting in partially hydrolyzing a nitrile of the general formula R-CN, wherein R represents an organic radical indiiferent to the action of sulphuric acid monohydrate, by sulphuric acid monohydrate in the presence of a catalyst containing a halide radical. I

13. A process consisting in partially h drolyzing a nitrile of the general formu a R--CN wherein R represents an organic radical, indifferent to the action of sulphuric acid monohydrate, by sul huric acid monohydrate in the presence 0 a catalyst containing a halide radical and while suspended in carbon tetrachloride.

Signed at Pittsburgh, in the countyof Allegheny and State of Pennsylvania, this 14th day of July, A. D. 1925.

' RALF B. TRUSLER. 

